Donald



Patented Dec. 7, 1926.

, DONALD e. ROGERS, on BUFFALO, new yonnnssrsnoa T NATIONAL ANILINE & CHEMICAL COMPANY, INC., on new YGRK, n. Y., A CORPORATION on NEW YORK.

rcaonncrion on VAT DYESTUFFS.

No Drawing.

This invention relates to the production of vat dyestuffs, and particularly to the dyestufi known chemically as N-dihydro- 1.2 1'2 anthraquinonazine from betaaminoanthraquinone.

In the fusion of beta-aminoanthraquinone, as heretofore proposed, for the production of N-dihydro-1.2-1.2'-anthraquinonazine, a

quantity of caustic'potash has been used greatly in excess of that required for the reaction. This large excess of caustic potash involves asubstantial element of expense and is undesirable from the standpoint ofyield of the final dye; but it has nevertheless been considered necessary to use such an excess of the caustic potash in order to give suflicient fluidity to the melt to allow suitable agitation at temperatures not too high forthe process in question.

The presentinvention is based upon the discovery that the amount of caustic potash required in the fusion of betaaminoanthraquinone for the production of 'N-dihydro 1.2-1;2-anthraquinonazine can be radically reduced in amount, and the fusion carried out in a'particularly advantageous manner by adding a suitable mineral oil to the reaction mass. I have found that by the use of mineral oil, the amount of caustic potash can be reducedto 40% or less of the amount heretofore'used. The mineral oil does not apparently enter into or. affect the course of thereaction in any objecionable way, and it maybe readily recovered and used over again. It nevertheless enables the fusion mass to be kept sufficiently fluid so that it may be suitably agitated.

In addition to the-advantage of greatly reducing the amount of caustic potash required the addition of mineral oil to the reaction mass considerably reduces the time required for the completion of the process, greatly simiplifies the operation'and' control of the process, ascompared with the process in which a large amount of causticpotash is used without themineral oil or'similar material, and produces a product which is in a high state-of subdivision. 4

The mineraloil employed should advantageously have a suitable boiling point of around 230 C. or somewhat higher, that is, at about the temperature at which the-process is to'be carried out. By using mineral oil of a boiling point corresponding to that r ofthe desired temperaturepf the reaction,

Application filed June 1 7, 1921. Serial No. 478,323.

it affords an automlatic temperature control of the reaction, inasmuch as the temperature will not exceed the boiling point of the mineral oil. A suitable mineral oil may be obtained from commercial kerosene by subjecting it to distillation and removing the fraction boiling below about 230 C. If steam distilled kerosene is used, the final 'dyestufl produced in the process can readily be freed from kerosene by steam distillation. Instead of using kerosene, other indifferent s'olvents or diluents can be used. for example, hydrocarbons which are liquid at relatively low temperatures and which have a boiling pointabove that of the temperature of reaction and which can be separated Without difliculty at the end of the reaction;

The invention will be further illustrated by the following specific example:

220 liters of mineral oil, obtained from steam distilled kerosene, of a boiling point somewhat above 230 C. are heated to a temperature of from 220 to 225 C., 40 kilos of beta-aminoanthraquinone are added with agitation, and then 7.5 kilos of potassium nitrate or chlorate. 30-35 kilos of potassium hydroxide in granular, flake or owdered form are then gradually added while maintaining the temperature around 220" to 225 C. The temperature is then raised to about 230 C. to complete the reaction which takes place with evolution of water vapor and with a change of color, passing from the orange of beta-aminoanthraquinone to the violet black of the condensation product. At the end of the reaction, the fusion-mass is cooled, the mineral oil filtered 011", and the product worked up in the man- 'ner usually employed for the isolation and purification of this'dyestufi'.

During the addition of the caustic pot-ash,

to the reaction mass, water vapor'is evolved, and the temperature is lowered slightly thereby. This water vapor shouldbe peraction can besuitably condensed and recovered.

In carrying out the process, the manner or order of admixlng the ingredlents can able for carrying out the process.

be varied somewhat, for eg ainple, the potassium hydrdxide and the potassium nitrate or chlorate may be added to the hot nineral oil, and the beta aniinoanthraquinone then added, or fa r nixtureof the -p'otassiurn hydroxide, potassium nitrate or chlorate, and. beta-aminoanthraquinone can be added [0 the hot oil.

Dillercnt forms of amiaratus {re ayailhe process thuscan beca-rrietlout, -for,example, in a jacketed ,viron fusionkettle provided with an agitator, thermometer ,Well, and a ater ja ket c ndense and ha g su ehle outlet at the bottom.

lfhe dyestuil' produced asabove described when freed from alkali and ini )urities, is characterized by great fineness o l grain, that is,; ii is obtained in a \y'ery finely divided state instead 01" large hard particles. The product is thusobtaincd in a physical condition ivhich nakes it of particular value for use .iIL'the productionofdye pastes and powders. llyepastes and powders made with theprodnet of the above process have thus shown much greater tinctorial power than dye pastes and powders produced by .the fusion of beta-aminoanihi-aqninone with caustic potash without the use of kerosene or similar niaterial unless the latter dye pastes and powders are specially after-treated.

In the process of-tlre abovespecific example;the amount of caustic potash employed is only about 15% of that required in carrying out the fusion when no hydrocarbon is 7 used while the time required ifor the completion of .the process is considerably less, for example being only about 6:5 minutes for the completion of the operation after beginning to add-the caustic potash as compared with about lihonrs or nore when no hydrocarbon is employed. The process of the present in- .rention also avoids objectionable io-.uni'ng .andenables the temperatu-re to .l-ie easily; 101% trolled. The process also goes on without appreciable loss of ammonia such as takes ,placein the usual fusion process. The tempenature .ot the reaction is also $Qmewhat lower than when ikerosene orsimilar ,rhydrocarbon is not used; while a somewhat increased yield of the desired product is obmined. V

It .Will ithus {he seen-that the present invent'ion; presents -manyadvantages orerythe proc- Easing ibetiuaminoanthraquinone with caus'ticipolash heretoforeknown, among these advantages being the radical reduction "lilltihfi amount of caustic .potash .used, a simplifioation in .the;operation of .:the process, .a cuttingidown (in the time required, :the prevention oif'frothing, ease of control of ithe temperature,.and :the production of increased yields of a. product in a granular form :instead ofiin the term of .hard Jumps; moreover, the duslon melt, before filtration, can

be .kept without bei g affected .by atmosphericconditions, itoeing protectedby the layer of mineral oil. These and other advantages are obtained by theuse inthe fus o P o es i a eeteri s ch as mi dyestnif as a new product. Thisprodnctcan he used without special trealmelit in.p1'i1it-' in and pigment words Moreover, the dye pastes containing it seem to havea greater vstability toward rnicromrganismsthan other simple water pastes, -.perha,ps.due toza small amount of kerosene still contained in vthe product in anemulsified condition.

Theiternflfusion is usedto referito the heating operation, whether or not actual nieltingof the ingmdientsor their solution .in-the So ven 0.1 cli uentdakes place.

I claim:

-1. fllhe improvement in the production of rat dyes Whichcomprises subjecting a betaaniinoanthn uinonje compound, to the aco o music a k lis n the Presenceof an ndi eren o entordiluent.

The improvements inztheiproduotionof vat dyes which comprises subjecting a beta.- .aminoanthraquinone compound, :10 'acdion of caustic potash xin thepresencevoi an indifferent solvent or diluent.

3. llhe improvement in .the prodnetiongoif N' -dihydro-l.i2121amtln-aguinonazirrby fusing b61121"fl mllIOIl'l'ItllLflLllllllQHQ .fvith caustic alkali WlUGll comprises carrying out the fusion with the additionof aniindifierent dil lle -llt rllquld fltithfl tBIDPGIZItIHEaOf the fusion and-with the use'gof a radically smaller amount of caustic alkali as compared with the amount required when such indifferent diluent isnot employed- ;4. The improvement .inthe production of N :dtlrvdro1ls2nlCQsanthraquinUnaZin byifusing ibetasaminoanthraquinone with caustic 1 alkali which comprises carn ingout .the furSlOll with the addition of adiydroearhon liquid at theteniperaitureofithe fnsionand with ithenee of a radically smaller. amount of =causticalkali as compared withthe amount r quired when such ihydroearbon' is not .em pluyed.

.5. Elihe improvement in ithe production of N-di'hydrod.2 12'-anthraquinonaain which comprises subjecti ,b t quL 7 5 none to fusion with caustic potash in the presence of a hydrocarbon or mixture of hydrocarbons which are liquid at ordinary temperatures and have a boiling point at or about the temperature of the fusion, whereby the reaction temperature is regulated by the boiling point of the solvent.

6. The improvement in the production of N-dihydro-1.2-1'.2-anthraquinonazin which comprises gradually adding caustic potash to 'a mixture of betaaminoanthraquinone and mineral oil and heating the resulting mixture to a temperature of about 230". C. to complete the reaction.

7. The improvement in the production of N-dihydro-l.2-1'.2-anthraquinonazin which comprises subjecting beta-aminoanthraquinone to the action of caustic potash in the presence of mineral oil at a temperature of about 230 C., the mineral oil having a boiling point of about 230 C. or above.

8. The improvement in the method of producin g N-dihydro-1.2-1.2'-anthraquinonazin which comprises gradually adding about kilos of caustic potash to a mixture of about 200 liters of mineral oil and 40 kilos of betaaminoanthraquinone at a temperature around 220 to 225 0., raising the temperature to around 230 C. to complete the reaction and permitting the water vapor evolved to escape from the reaction mass.

9. The improvement in the production of N-dihydro-L2-1'.2-anthraquinonazin which comprises subjecting beta-aminoanthraquinone to fusion with caustic alkali in the presence of an organic liquid chemically inactive under the conditions of the fusion, whereby the amount of caustic alkali is greatly reduced from that required when such organic liquid is not employed.

10. As a new product, N-dihydro-1.2-l.2- anthraquinonazin in a finely divided and defiocculated condition, resulting from the fusion of beta-aminoanthraquinone with caustic alkali in the presence of an indifferent diluent liquid at the temperature of reaction and at the temperature of the separation of the product therefrom.

11. The process of making indanthrene blue by heating beta amino-anthraquinone with caustic potash and kerosene.

12. The process of making indanthrene blue by adding caustic potash at 220 0., to beta aminoranthraquinone suspended in kerosene.

13. The process of making indanthrene blue by heating beta-amino-anthraquinone and caustic potash at about 230 C. in the presence of an inert hydrocarbon diluent.

14. The process producing indanthrene blue by first suspending or dissolving beta amino-anthraquinone in a mineral oil material, and then subjecting it to the action of caustic potash at about 230 C.

15. The process of making indanthrene blue by the fusion of beta amino anthraquinone at about 230 C., with caustic potash suspended in kerosene and removing with the kerosene vapor the water-vapors evolved in the reaction.

In testimony whereof I afiiX my signature.

DONALD G. ROGERS. 

